WO2018135685A1 - Méthode de production de particules creuses de silice à partir de silicate de sodium à l'aide de particules de gabarit inorganique de zno - Google Patents

Méthode de production de particules creuses de silice à partir de silicate de sodium à l'aide de particules de gabarit inorganique de zno Download PDF

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WO2018135685A1
WO2018135685A1 PCT/KR2017/001119 KR2017001119W WO2018135685A1 WO 2018135685 A1 WO2018135685 A1 WO 2018135685A1 KR 2017001119 W KR2017001119 W KR 2017001119W WO 2018135685 A1 WO2018135685 A1 WO 2018135685A1
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zno
particles
inorganic template
silica
particle
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PCT/KR2017/001119
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Korean (ko)
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이성의
이지선
이영철
노경재
김용우
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한국산업기술대학교산학협력단
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Publication of WO2018135685A1 publication Critical patent/WO2018135685A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

Definitions

  • the present invention relates to a method for producing hollow silica particles from sodium silicate using ZnO inorganic template particles, and more particularly, to preparing hollow silica particles by synthesizing ZnO as an inorganic template particle and using sodium silicate as a silica precursor. It is about a method.
  • the hollow inorganic particles have a hollow shape in which shells containing nano pores are surrounded by outer shells.
  • Micro and nano-sized hollow inorganic particles have high application potential in academic and industrial fields due to their unique physical properties such as relatively low density, large specific surface area and surface permeability.
  • silica produced from TEOS is coated on the surface of the organic mold to form a core shell structure primarily, and finally, hollow silica particles may be obtained by removing the organic template using heat treatment or an organic solvent.
  • An object of the present invention is to provide a method for producing hollow silica particles from sodium silicate using a ZnO inorganic template that can be easily removed through an acid treatment process without using a separate firing process or an organic solvent.
  • Another object of the present invention to control the shape and size of the ZnO inorganic template particles to produce hollow silica particles having a variety of shapes and various hollow sizes to provide hollow silica particles required according to the application.
  • ZnO inorganic template particles according to the present invention are characterized in that it comprises the steps of mixing the Zn precursor and the alkaline precipitating agent and applying heat to the solution.
  • the Zn precursor is characterized in that any one of zinc chloride (ZnCl 2 ), zinc acetate (Zn (CH 3 COO) 2 ).
  • the Zn precursor is zinc chloride (ZnCl 2 )
  • the alkaline precipitant is NaOH, LiOH, NaCO 3
  • the ZnO inorganic template particles are characterized in that the sphere of 190nm to 200nm diameter.
  • the Zn precursor is zinc chloride (ZnCl 2 )
  • the alkaline precipitant is NaOH
  • the ZnO inorganic template particles are characterized in that the particle size of 200nm to 300nm plate-shaped.
  • the Zn precursor is zinc chloride (ZnCl 2 )
  • the alkaline precipitant is NaOH
  • the ZnO inorganic template particles are characterized in that the columnar shape of 500nm to 2.0 ⁇ m.
  • the Zn precursor is zinc chloride (ZnCl 2 )
  • the alkaline precipitant is characterized in that NH 4 OH.
  • the ZnO inorganic template particles are characterized in that the plate-shaped of 0.4 ⁇ m to 1.0 ⁇ m.
  • the ZnO inorganic template particles are characterized in that the oval having a particle length of 2.0 ⁇ m to 3.0 ⁇ m.
  • the method may further include dispersing the ZnO inorganic template particles by applying ultrasonic waves to a solution in which the heated Zn precursor and the alkaline precipitant are mixed.
  • Hollow silica particles according to the present invention is heated to a solution mixed with a Zn precursor and an alkaline precipitant to prepare a ZnO inorganic template particles (S100), by reacting the silica precursor and salt with the ZnO inorganic template particles Forming a silica shell on the surface of the ZnO inorganic template particles to prepare ZnO / silica core-shell particles (S200) and removing the ZnO inorganic template particles from the ZnO / silica core-shell particles (S300) Characterized in that it comprises a.
  • the silica precursor of step S200 is characterized in that the sodium silicate (sodi ⁇ m silicate).
  • the concentration of the sodium silicate is characterized in that 0.2 M to 0.6 M.
  • the salt of the step S200 is (NH 4 ) 2 SO 4 Or NaH (CO 3 ) 2 .
  • reaction temperature for forming the ZnO / silica core-shell particles of the step S200 is characterized in that 60 °C to 90 °C.
  • the removal of the ZnO inorganic template particles in the step S300 is performed by dispersing the core shell particles of ZnO / silica in distilled water, stirring and dropping the acid solution to dissolve the ZnO inorganic template particles. It features.
  • the acid (acid) solution is characterized in that any one of dilute hydrochloric acid solution or sulfate diluent.
  • the present invention through the above problem solving means to produce hollow silica particles using ZnO inorganic template particles that can be easily removed through the acid treatment process without using a separate heat treatment or organic solvent, heat treatment and organic solvent Particle agglomeration and contamination can be prevented during the mold particle removal process.
  • the size and shape of the ZnO inorganic mold particles can be controlled to maximize the hollow size of the hollow silica and improve the hollow efficiency. Particles can be provided.
  • reaction solvent is water
  • TEOS TEOS
  • FIG. 1 is a flow chart showing a manufacturing process of hollow silica particles according to the present invention.
  • Figure 2 is a schematic diagram showing a process of forming hollow silica particles according to the present invention.
  • Figure 3 is a flow chart showing a process for producing a ZnO inorganic template particles according to the present invention.
  • 4A and 4B are SEM images showing ZnO inorganic template particles according to the type of ZnO precursor.
  • 5A, 5B, and 5C are SEM images of ZnO inorganic template particles according to concentrations of ZnO precursors.
  • 6A, 6B, and 6C are SEM images showing ZnO inorganic template particles according to the type of alkaline precipitant.
  • FIG. 7 are SEM images showing ZnO inorganic template particles according to pH.
  • FIG. 8 are SEM images showing ZnO inorganic template particles according to reaction temperature.
  • FIG. 9 is an SEM image showing an elliptical ZnO inorganic template particle according to the present invention.
  • FIG. 10 is a SEM image of the spherical ZnO inorganic template particles of 0.1 ⁇ m to 0.2 ⁇ m size according to the present invention.
  • FIG. 11 is an SEM image of a cross section of a coating film after coating hollow silica synthesized using spherical ZnO inorganic template particles having a size of 0.1 ⁇ m to 0.2 ⁇ m on a substrate.
  • FIG. 1 is a flow chart showing a manufacturing process of hollow silica particles according to the present invention.
  • a ZnO inorganic template particle is prepared by applying heat to a solution in which a Zn precursor and an alkaline precipitant are mixed (S100), and a silica precursor and a salt of the ZnO inorganic template particle. Reacting to form a silica shell on the surface of the ZnO inorganic template particles to produce ZnO / silica core-shell particles (S200) and to remove the ZnO inorganic template particles from the ZnO / silica core-shell particles It characterized in that it comprises a step (S300).
  • the ZnO inorganic template particles become the basic skeleton of the hollow silica particles, controlling the shape of the ZnO inorganic template particles affects the shape of the hollow silica particles.
  • the Zn precursor and the alkaline precipitant are mixed using a sedimentation method, and then reacted with heat to form ZnO inorganic template particles.
  • the Zn precursor may be zinc chloride (ZnCl 2 ), zinc acetate (Zn (CH 3 COO) 2 ), and the like
  • the alkaline precipitant may be NaOH, LiOH, NaCO 3 , NH 4 OH, or the like.
  • the shape and size of the ZnO inorganic template particles may be determined by the type of Zn precursor, Zn precursor concentration, type of alkaline precipitant, pH, reaction temperature, and the like.
  • the shape and size of the ZnO inorganic template particles are the biggest factor in determining the shape and hollow efficiency of the hollow silica, and it is important to control and control them.
  • the size and shape of the ZnO particles can be adjusted according to the type of Zn precursor. This is because the reaction mechanism is the same, but the reaction rates with salts and precipitants produced during the reaction are different.
  • zinc chloride has a faster reaction rate with a precipitant than zinc acetate, so that the particle size increases as the particle formation proceeds faster.
  • the higher the concentration of the Zn precursor in the Zn precursor concentration the larger the particle size.
  • the lower the concentration the slower the nucleation rate, and therefore, the smaller the agglomeration between the formed nuclei and the smaller the particle size.
  • 100 nm spherical particles are formed in zinc chloride 0.5M, and 200 nm spherical particles are formed in zinc choride 1.5M.
  • the shape and size of the ZnO template particles may vary depending on the type of alkaline precipitant.
  • sodium hydroxide (NaOH) lithium hydroxide (LiOH), sodium carbonate (Na 2 CO 3 )
  • spherical particles of several nanometers are formed, and when using ammonium hydroxide ((NH 4 ) OH), unlike other precipitants Particles on the order of micrometers can be formed, and long oval or plate-shaped ZnO inorganic template particles can be obtained.
  • the particles grow in the crystal c-axis direction, which is a direction for reducing the surface energy of the particles, thereby forming ZnO close to the plate rather than the spherical particles.
  • the pH of the reaction solvent increases, the particles grow in the crystal c-axis direction, which is a direction for reducing the surface energy of the particles, thereby forming ZnO close to the plate rather than the spherical particles.
  • plate-shaped particles are formed.
  • the spherical particle size increases, and in the case of plate particles, columnar particles are formed by growing in the c-axis direction.
  • the particle size increases significantly above the reaction temperature of 70 °C.
  • FIG. 1 is a flow chart showing a manufacturing process of hollow silica particles according to the present invention.
  • a ZnO inorganic template particle is prepared by applying heat to a solution in which a Zn precursor and an alkaline precipitant are mixed (S100), and a silica precursor and a salt of the ZnO inorganic template particle. Reacting to form a silica shell on the surface of the ZnO inorganic template particles to produce ZnO / silica core-shell particles (S200) and to remove the ZnO inorganic template particles from the ZnO / silica core-shell particles It characterized in that it comprises a step (S300).
  • the ZnO inorganic template particles become the basic skeleton of the hollow silica particles, controlling the shape of the ZnO inorganic template particles affects the shape of the hollow silica particles.
  • the Zn precursor and the alkaline precipitant are mixed using a sedimentation method, and then reacted with heat to form ZnO inorganic template particles.
  • the Zn precursor may be zinc chloride (ZnCl 2 ), zinc acetate (Zn (CH 3 COO) 2 ), and the like
  • the alkaline precipitant may be NaOH, LiOH, NaCO 3 , NH 4 OH, or the like.
  • the shape and size of the ZnO inorganic template particles may be determined by the type of Zn precursor, Zn precursor concentration, type of alkaline precipitant, pH, reaction temperature, and the like.
  • the shape and size of the ZnO inorganic template particles are the biggest factor in determining the shape and hollow efficiency of the hollow silica, and it is important to control and control them.
  • the size and shape of the ZnO particles can be adjusted according to the type of Zn precursor. This is because the reaction mechanism is the same, but the reaction rates with salts and precipitants produced during the reaction are different.
  • zinc chloride has a faster reaction rate with a precipitant than zinc acetate, so that the particle size increases as the particle formation proceeds faster.
  • the higher the concentration of the Zn precursor in the Zn precursor concentration the larger the particle size.
  • the lower the concentration the slower the nucleation rate, and therefore, the smaller the agglomeration between the formed nuclei and the smaller the particle size.
  • 100 nm spherical particles are formed in zinc chloride 0.5M, and 200 nm spherical particles are formed in zinc choride 1.5M.
  • the shape and size of the ZnO template particles may vary depending on the type of alkaline precipitant.
  • sodium hydroxide (NaOH) lithium hydroxide (LiOH), sodium carbonate (Na 2 CO 3 )
  • spherical particles of several nanometers are formed, and when using ammonium hydroxide ((NH 4 ) OH), unlike other precipitants Particles on the order of micrometers can be formed, and long oval or plate-shaped ZnO inorganic template particles can be obtained.
  • the particles grow in the crystal c-axis direction, which is a direction for reducing the surface energy of the particles, thereby forming ZnO close to the plate rather than the spherical particles.
  • the pH of the reaction solvent increases, the particles grow in the crystal c-axis direction, which is a direction for reducing the surface energy of the particles, thereby forming ZnO close to the plate rather than the spherical particles.
  • plate-shaped particles are formed.
  • the spherical particle size increases, and in the case of plate particles, columnar particles are formed by growing in the c-axis direction.
  • the particle size increases significantly above the reaction temperature of 70 °C.
  • the silica precursor and the ammonium salt or the metal salt are simultaneously dropped in a solution in which the ZnO inorganic template particles are dispersed, and the ZnO inorganic template A silica shell is formed on the surface of the particles to obtain core shell particles of ZnO / silica.
  • the silica precursor may be sodium silicate (Sodi ⁇ m Silicate)
  • the ammonium salt or metal salt may be ammonium sulfate ((NH 4 ) 2 SO 4 ), sodium bicarbonate (NaH (CO 3 ) 2 ). have.
  • the ZnO inorganic template particles are agglomerated or precipitated, the content of the silica precursor is increased compared to the surface area of the ZnO inorganic template particles. This is because a silica shell of one thickness or shape cannot be formed. Accordingly, it is required that all ZnO inorganic template particles be used in the core shell reaction by applying ultrasonic waves so that the ZnO inorganic template particles in the solution can be well dispersed. In one embodiment, the ultrasound may be applied for about 20 minutes at a frequency of about 40 kHz.
  • the shell thickness and shape of the hollow silica may be controlled by the size and shape of the ZnO inorganic template particles, the dispersion degree of the ZnO inorganic template particles, the concentration and the reaction temperature of the silica precursor, and the like.
  • the hollow efficiency can be expanded by controlling the thickness of the silica shell formed by lowering the concentration of the silica precursor.
  • the silica precursor concentration is extremely low, the amount of generated silica is insufficient compared to the surface area of the surface of the ZnO inorganic template particle, so that the hollow silica is formed in the form of broken silica shell.
  • an appropriate concentration of silica precursor is added.
  • the shell formation was best formed at about 0.2M of sodium silicate. At concentrations below 0.2M, the shells form broken, above 0.2M, the shell thickness gradually increases, and above 0.6M, unwanted spherical silica particles form on the shell surface.
  • the reaction temperature when the reaction temperature is low based on the same reaction time when forming the silica shell, the size of the silica spherical particles constituting the silica shell is small, it is possible to control the shell thickness thinly.
  • the reaction temperature if the reaction temperature is too low, the reaction rate of shell formation is slowed down, and thus the silica is not coated on the surface of the ZnO inorganic mold, thereby forming a hollow hollow silica.
  • the reaction temperature when the reaction temperature is high, the shell formation reaction rate may be increased, and thus the silica shell may be easily formed on the surface of the ZnO inorganic mold. have.
  • the shell is formed in a broken form at a reaction temperature of 60 ° C. or lower, and the shell is formed well at a temperature of 60 ° C. or higher, but the shell surface becomes rough at 90 ° C. or higher.
  • the reaction temperature is preferably adjusted according to the added ZnO inorganic template size and silica precursor concentration, and by controlling the size of the silica spherical particles constituting the silica shell by controlling the reaction temperature, it is possible to ultimately control the hollow silica shell thickness.
  • the step S300 of removing the ZnO inorganic template particles will be described.
  • the acid solution is added dropwise at room temperature while stirring to form hollow silica by melting the ZnO inorganic template particles.
  • the acid solution may be dilute hydrochloric acid or dilute sulfate.
  • the hollow silica dispersion from which the ZnO inorganic template particles have been removed is washed with distilled water using a filter, and finally, the hollow silica particles are obtained.
  • the core in the silica shell can be easily removed using an acid solution, hollow silica particles can be manufactured by a simple method without undergoing a calcination process or an extraction process using an organic solvent.
  • Figure 2 is a schematic diagram showing a process of forming hollow silica particles according to the present invention.
  • (a), (b) and (c) show a process in which the silica precursor forms a silica shell on the surface of the ZnO inorganic template particle to form ZnO / silica coreshell particles, and (d) shows a coreshell of the formed ZnO / silica.
  • Hollow silica particles are formed by removing ZnO inorganic template particles from the particles.
  • 4A and 4B are SEM images showing ZnO inorganic template particles according to the type of Zn precursor.
  • 5A, 5B, and 5C are SEM images of ZnO inorganic template particles according to concentrations of ZnO precursors.
  • 6A, 6B, and 6C are SEM images showing ZnO inorganic template particles according to the type of alkaline precipitant.
  • FIG. 7 are SEM images showing ZnO inorganic template particles according to pH.
  • the sphere is formed at 200 nm in size, but when the pH is increased to 12 or 13, it can be seen that the plate is formed at 200 to 300 nm in size.
  • Specific experimental conditions are shown in Table 4 below.
  • FIG. 8 are SEM images showing ZnO inorganic template particles according to reaction temperature.
  • FIG. 9 is an SEM image showing an elliptical ZnO inorganic template particle according to the present invention.
  • the size of the elliptical ZnO inorganic template particles formed through the experiment was 2 to 3 micrometers ( ⁇ m). Specific experimental conditions are shown in Table 6 below.
  • Figure 11 is a SEM image of the cross section of the hollow silica.
  • ZnO inorganic template particles were prepared in a spherical shape so as to have a diameter of 0.1 to 0.2 ⁇ m.
  • 11 is a cross-sectional SEM image of a hollow silica formed using the spherical ZnO inorganic template particles (0.1 to 0.2 ⁇ m) to the substrate and then coated.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)

Abstract

La présente invention concerne une méthode de production d'une particule de silice creuse, la méthode comprenant : une étape de production d'une particule de gabarit inorganique de ZnO par application de chaleur à une solution obtenue par mélange d'un précurseur de Zn et d'un précipitant alcalin; une étape de production d'une particule cœur-écorce ZnO/silice par formation d'une écorce de silice sur la surface de la particule de gabarit inorganique de ZnO, par réaction d'un précurseur de silice et d'un sel avec la particule de gabarit inorganique de ZnO; et une étape d'élimination de la particule de gabarit inorganique de ZnO de la particule cœur-écorce ZnO/silice. La méthode de la présente invention produit une particule de silice creuse en utilisant une particule de gabarit inorganique de ZnO qui peut être facilement retirée par un procédé de traitement acide sans effectuer un traitement thermique séparé ou à l'aide d'un solvant organique, et peut ainsi empêcher des problèmes de contamination et de coagulation de particules qui se produisent au cours d'un processus d'élimination d'une particule de gabarit à l'aide d'un solvant organique et d'un traitement thermique. De plus, la méthode de la présente invention améliore l'efficacité d'évidement en maximisant la taille de la cavité de silice creuse en régulant la taille et la forme d'une particule de gabarit inorganique de ZnO, et peut fournir la particule de silice creuse qui est requise selon le domaine d'application.
PCT/KR2017/001119 2017-01-23 2017-02-02 Méthode de production de particules creuses de silice à partir de silicate de sodium à l'aide de particules de gabarit inorganique de zno WO2018135685A1 (fr)

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CN111607127A (zh) * 2020-06-09 2020-09-01 江西宝弘纳米科技有限公司 一种橡胶硫化活性剂及其制备方法和应用
CN115175873A (zh) * 2020-02-28 2022-10-11 协和化学工业株式会社 中空粒子、树脂组合物以及使用了该树脂组合物的树脂成型体和层叠体

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN115175873A (zh) * 2020-02-28 2022-10-11 协和化学工业株式会社 中空粒子、树脂组合物以及使用了该树脂组合物的树脂成型体和层叠体
CN111607127A (zh) * 2020-06-09 2020-09-01 江西宝弘纳米科技有限公司 一种橡胶硫化活性剂及其制备方法和应用

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